CN114762831B - Preparation method and preparation system of catalytic cracking auxiliary agent - Google Patents

Preparation method and preparation system of catalytic cracking auxiliary agent Download PDF

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Publication number
CN114762831B
CN114762831B CN202110028578.8A CN202110028578A CN114762831B CN 114762831 B CN114762831 B CN 114762831B CN 202110028578 A CN202110028578 A CN 202110028578A CN 114762831 B CN114762831 B CN 114762831B
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phosphorus
molecular sieve
catalytic cracking
aluminum
process according
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CN114762831A (en
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罗一斌
欧阳颖
王成强
邢恩会
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN202110028578.8A priority Critical patent/CN114762831B/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to PCT/CN2022/071280 priority patent/WO2022148471A1/en
Priority to EP22736632.5A priority patent/EP4275789A1/en
Priority to KR1020237027323A priority patent/KR20230130708A/en
Priority to JP2023541771A priority patent/JP2024502195A/en
Priority to TW111101188A priority patent/TW202237269A/en
Priority to CN202280009687.8A priority patent/CN116917234A/en
Priority to US18/260,971 priority patent/US20240059630A1/en
Publication of CN114762831A publication Critical patent/CN114762831A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a preparation method of a catalytic cracking auxiliary agent, which is characterized by comprising the following steps: the MFI molecular sieve with the temperature of 0-150 ℃ and the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ are subjected to impregnation treatment to obtain a phosphorus-modified MFI molecular sieve, a binder and optionally added second clay, and the mixture is mixed, beaten and molded; carrying out hydrothermal roasting treatment on the molded product under external pressure and an atmosphere environment of externally added aqueous solution; the apparent pressure of the hydrothermal roasting treatment is 0.01-1.0 Mpa and the water vapor is 1-100%; the hydrothermal roasting treatment is carried out at 200-800 ℃. The invention optimizes and shortens the preparation flow of the catalyst, and can reduce the preparation cost, and the prepared catalytic cracking auxiliary agent has good cracking conversion rate, low-carbon olefin yield and higher liquefied gas yield.

Description

Preparation method and preparation system of catalytic cracking auxiliary agent
Technical Field
The invention relates to a preparation method and a preparation system of a catalytic cracking auxiliary agent, in particular to a short-flow preparation method and a preparation system of a catalytic cracking auxiliary agent of a phosphorus-containing modified MFI molecular sieve.
Background
ZSM-5 molecular sieve was a widely used zeolite molecular sieve catalytic material developed by the company Mobil in 1972. The molecular sieve has a three-dimensional crossed pore canal structure, the pore canal along the axial direction a is a straight pore, the cross-sectional dimension of the pore canal along the axial direction b is 0.54 multiplied by 0.56nm, the pore canal along the axial direction b is a Z-shaped pore, the cross-sectional dimension of the pore canal along the axial direction b is 0.51 multiplied by 0.56nm, and the pore canal is elliptical. The ZSM-5 molecular sieve pore is composed of ten-membered rings, and the pore size is between that of small pore zeolite and large pore zeolite, so that the ZSM-5 molecular sieve has unique shape selective catalytic effect. The ZSM-5 molecular sieve has unique pore structure, good shape selective catalysis and isomerization performance, high heat and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon formation, is widely used as a catalyst and a catalyst carrier, and is successfully used in the production processes of alkylation, isomerization, disproportionation, catalytic cracking, methanol to gasoline, methanol to olefin and the like. ZSM-5 molecular sieve is introduced into catalytic cracking and carbon four hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin by utilizing the molecular shape selectivity of the molecular sieve.
Since 1983, ZSM-5 molecular sieves have been applied to catalytic cracking processes as an aid to the octane number of catalytic cracking, with the aim of increasing the octane number of catalytically cracked gasoline and the selectivity to lower olefins. In US3758403, it was first reported that ZSM-5 was used as an active component for propylene yield increase and REY was used to prepare FCC catalysts, and US5997728 discloses that ZSM-5 molecular sieves, which were not modified in any way, were used as an auxiliary agent for propylene yield increase, and that the propylene yields were not high. Although ZSM-5 molecular sieves have good shape selectivity and isomerization properties, they have the disadvantage of poor hydrothermal stability and are susceptible to deactivation under severe high-temperature hydrothermal conditions, leading to a reduction in catalytic performance.
In the 80 s of the 20 th century, the Mobil company found that phosphorus improved the hydrothermal stability of ZSM-5 molecular sieves and improved the yield of lower olefins by modifying ZSM-5 molecular sieves with phosphorus. Conventional additives typically contain phosphorus-activated ZSM-5, which selectively converts primary cracked products (e.g., gasoline olefins) to C3 and C4 olefins. After the ZSM-5 molecular sieve is synthesized, a proper amount of inorganic phosphorus compound is introduced for modification, so that framework aluminum can be stabilized under severe hydrothermal conditions.
In CN106994364a process is disclosed for the modification of ZSM-5 molecular sieves by first mixing a high alkali metal ion content ZSM-5 molecular sieve with one or more phosphorus containing compounds selected from the group consisting of phosphoric acid, diammonium hydrogen phosphate, monoammonium dihydrogen phosphate and ammonium phosphate to obtain a mixture having a phosphorus loading of at least 0.1wt% calculated as P2O5, drying, calcining the mixture, and then performing an ammonium exchange step and a water wash step to reduce the alkali metal ion content to below 0.10wt%, followed by a drying and hydrothermal aging step at 400-1000 ℃ and 100% steam. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity, and higher liquefied gas yield.
In CN1506161a, a method for modifying a hierarchical pore ZSM-5 molecular sieve is disclosed, which comprises the following conventional steps: synthesizing, filtering, carrying out ammonium exchange, drying and roasting to obtain a hierarchical pore ZSM-5 molecular sieve, modifying the hierarchical pore ZSM-5 molecular sieve by phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve, wherein the P2O5 loading amount is generally in the range of 1-7wt%. However, phosphoric acid or ammonium phosphate salts can self-polymerize to form phosphorus species with different aggregation states in the roasting process, and only phosphate radicals entering holes interact with framework aluminum to retain B acid centers in the hydrothermal treatment process, so that the distribution of the phosphorus species is reduced.
Although proper inorganic phosphide is adopted to modify ZSM-5 molecular sieve, which can slow down the dealumination of the framework and improve the hydrothermal stability, and phosphorus atoms can combine with distorted four-coordination framework aluminum to generate weak B acid centers, so that higher conversion rate of long-chain alkane pyrolysis and higher light olefin selectivity are achieved, excessive inorganic phosphide is used to modify ZSM-5 molecular sieve, which can block pore channels of molecular sieve, reduce pore volume and specific surface area and occupy a large amount of strong B acid centers. In addition, phosphoric acid or ammonium phosphate salt in the roasting process can self-polymerize to generate phosphorus species with different aggregation states, the coordination of phosphorus and framework aluminum is insufficient, the utilization efficiency of phosphorus is low, and the modification of phosphorus does not always obtain satisfactory hydrothermal stability improvement results. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus modified ZSM-5 molecular sieve and further improve the cracking activity.
In the industrial production of the prior art, the preparation flow of the catalytic cracking auxiliary agent is shown in figure 1, and the MFI molecular sieve is subjected to phosphorus modification treatment (phosphorus-containing solution impregnation treatment), drying, primary roasting, mixing and forming (spray drying) of raw materials including the molecular sieve and a binder, and secondary roasting to obtain a cracking auxiliary agent finished product. In order to improve the hydrothermal stability of the MFI molecular sieve treated by phosphorus modification, the prior art needs to carry out two roasting processes, and has high preparation cost and complex flow.
Disclosure of Invention
The invention provides a preparation method of a catalytic cracking auxiliary agent, which aims at solving the problems that in the prior art, the phosphorus modification process of an MFI molecular sieve in order to improve the hydrothermal stability of the MFI molecular sieve is complex and the preparation process of the auxiliary agent is complex.
It is a second object of the present invention to provide a preparation system for the above simplified flow process preparation method.
In order to achieve one of the above objects, the present invention provides a method for preparing a catalytic cracking auxiliary agent, which is characterized in that the method comprises: the MFI molecular sieve with the temperature of 0-150 ℃ and the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ are subjected to impregnation treatment to obtain a phosphorus-modified MFI molecular sieve, a binder and optionally added second clay, and the mixture is mixed, beaten and molded; carrying out hydrothermal roasting treatment on the molded product under external pressure and an atmosphere environment of externally added aqueous solution; the apparent pressure of the hydrothermal roasting treatment is 0.01-1.0 Mpa and the water vapor is 1-100%; the hydrothermal roasting treatment is carried out at 200-800 ℃.
In the preparation method provided by the invention, the catalytic cracking auxiliary agent contains 5-75 wt% of phosphorus modified MFI molecular sieve, 1-40 wt% of binder and 0-65 wt% of second clay on a dry basis.
In the preparation method provided by the invention, the phosphorus-containing compound used for phosphorus modification can be selected from organic phosphorus compounds and/or inorganic phosphorus compounds. The organic phosphorus compound may be selected from, for example, trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphorus bromide, triphenyl butyl phosphorus bromide, triphenyl benzyl phosphorus bromide, hexamethylphosphoric triamide, dibenzyldiethyl phosphorus, 1, 3-xylene bis triethyl phosphorus; the inorganic phosphide may be selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, boron phosphate, for example.
In the preparation method provided by the invention, in the MFI molecular sieve, na 2 O<0.1wt％。
In the preparation method provided by the invention, the phosphorus modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multistage hole ZSM-5 molecular sieve. The mole ratio of silicon oxide/aluminum oxide of the microporous ZSM-5 molecular sieve is 15-1000, preferably 20-200. The ratio of mesoporous volume to total pore volume of the multistage hole ZSM-5 molecular sieve is more than 10%, the average pore diameter is 2-20 nm, and the mol ratio of silicon oxide to aluminum oxide is 15-1000, preferably 20-200.
In the preparation method, when the MFI molecular sieve is subjected to impregnation treatment by using a water solution of a phosphorus-containing compound, the phosphorus-containing compound is calculated by phosphorus, and the MFI molecular sieve is calculated by aluminum, and the molar ratio of the phosphorus-containing compound to the MFI molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2-1.5. The weight ratio of the water sieve is 0.5-1; the impregnation treatment is preferably carried out at a higher temperature, preferably 50-150 c, more preferably 70-130 c, for 0.5-40 hours, since a higher impregnation treatment temperature is advantageous for obtaining a better effect, i.e. better dispersion of phosphorus species, more easily migrates into the molecular sieve during the subsequent pressure roasting of the catalyst raw material mixture to bind with framework aluminum, further increasing the degree of coordination of phosphorus with framework aluminum and eventually increasing the hydrothermal stability of the molecular sieve.
In the preparation method of the invention, the apparent pressure of the atmosphere environment is 0.1-0.8 Mpa, preferably 0.3-0.6 Mpa, and the atmosphere environment contains 30-100% of water vapor, preferably 60-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃. The external pressure is applied to the molded product of the auxiliary raw material mixture from the outside in the hydrothermal roasting treatment process, and for example, inert gas is introduced from the outside to maintain a certain back pressure. The external water is added in an amount which satisfies the condition that the atmosphere contains 1 to 100 percent of water vapor.
In the preparation method, the binder is at least one selected from pseudo-boehmite, aluminum sol, silicon aluminum sol, water glass and phosphorus aluminum inorganic binder; the preferred binder comprises a phosphorus aluminum inorganic binder, and the more preferred binder is a phosphorus aluminum inorganic binder. The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay. When the house is atWhen the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay, the phosphorus-aluminum inorganic binder containing first clay is based on dry basis, and the phosphorus-aluminum inorganic binder containing first clay contains Al 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio containing the first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.
In the preparation method provided by the invention, the second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.
In the preparation method provided by the invention, a specific implementation mode of the composition of the binder comprises 3-39 wt% of the phosphorus-aluminum inorganic binder based on the total amount of the catalytic cracking auxiliary agent and 1-30 wt% of other inorganic binders based on the dry basis, wherein the other inorganic binders comprise at least one of pseudo-boehmite, aluminum sol, silicon-aluminum sol and water glass.
In the preparation method provided by the invention, preferably, the phosphorus-aluminum inorganic binder containing the first clay is prepared by the following steps: pulping and dispersing an alumina source, the first clay and water into slurry with a solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide is prepared by 15 to 40 weight parts of aluminum oxide 2 O 3 An alumina source in an amount of greater than 0 parts by weight and no more than 40 parts by weight, based on dry weight of the first clay; adding concentrated phosphoric acid to the slurry with stirring according to the weight ratio of P/Al=1-6, and reacting the obtained mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus in phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
In the preparation method provided by the invention, the microsphere with the diameter of 1-150um is obtained by spray drying granulation molding, and the operation is well known to the person skilled in the art and is not repeated here.
The invention also provides the catalytic cracking auxiliary agent prepared by the method.
The invention further provides a method for catalytic cracking of hydrocarbon oil, which is characterized by comprising the following steps: and (3) under the catalytic cracking condition, the hydrocarbon oil is contacted and reacted with the catalytic cracking auxiliary agent.
The invention provides a cracking method, which comprises the following steps: contacting the hydrocarbon oil with a catalyst mixture comprising the catalytic cracking aid and a catalytic cracking catalyst under the catalytic cracking conditions; the content of the catalytic cracking auxiliary agent in the catalyst mixture is 0.1-30 wt%.
In the cracking method provided by the invention, the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, direct-current wax oil, light/heavy propane deoiling, coker wax oil and coal liquefied products.
In order to achieve the second purpose, the invention provides a preparation system of a catalytic cracking auxiliary agent, which is characterized by mainly comprising a phosphorus modification device of an MFI molecular sieve, a raw material mixing device, a forming device and a pressurized water heating roasting device.
In the preparation system, the phosphorus modification device of the MFI molecular sieve is used for the impregnation treatment operation of the phosphorus-containing compound solution and the MFI molecular sieve, and comprises phosphorus-containing compound solution introducing equipment.
In the preparation system of the invention, the raw material mixing device receives raw materials of preparation auxiliary agents including the impregnated phosphorus modified MFI molecular sieve obtained from the phosphorus modification device of the MFI molecular sieve, the phosphorus-aluminum inorganic binder from the phosphorus-aluminum inorganic binder treatment device and the optionally added clay.
In the production system of the present invention, the forming device is preferably a spray-drying forming device.
In the preparation system, the hydrothermal pressurized roasting device is provided with a water input port and a gas pressurizing interface so as to meet the pressurized hydrothermal roasting condition of the formed product.
One particular form of the preparation system provided by the present invention is shown in fig. 2. As can be seen from fig. 2, in the phosphorus modification device of the MFI molecular sieve, the MFI molecular sieve is subjected to impregnation treatment with a phosphorus-containing solution to obtain a phosphorus-modified MFI molecular sieve; in the raw material mixing device, raw materials including a phosphorus modified MFI molecular sieve, a binder, optional second clay and the like are mixed and pulped and molded (spray-dried); the molded article is subjected to pressurized hydrothermal baking treatment under an atmosphere of externally applied pressure and externally added water.
The preparation method provided by the invention has the advantages that the preparation process of the cracking auxiliary agent is optimally shortened, the preparation cost can be reduced, and the catalytic cracking auxiliary agent provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbon, and simultaneously has higher liquefied gas yield.
Drawings
FIG. 1 is a flow chart of a conventional catalyst preparation in the prior art.
FIG. 2 is a flow chart of a catalyst preparation system provided by the invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The apparatus and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The micro-reaction device is adopted to evaluate the influence of the catalytic cracking auxiliary agent of the invention on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon.
And (3) carrying out 800 ℃ and 100% water vapor aging treatment on the prepared catalytic cracking auxiliary sample on a fixed bed aging device for 17 hours, and evaluating on a micro-reaction device, wherein the raw oil is VGO or naphtha, and the evaluation condition is that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the catalyst-oil ratio is 3.2. Microreaction activity was measured using ASTM D5154-2010 standard method.
Some of the raw materials used in the examples were as follows:
pseudo-boehmite is an industrial product produced by Shandong aluminum company and has a solid content of 60 weight percent. The aluminum sol is an industrial product produced by the middle petrochemical catalyst Qilu division company, al 2 O 3 The content was 21.5% by weight. Silica sol is an industrial product produced by the middle petrochemical catalyst Qilu division company, siO 2 The content was 28.9 wt%, na 2 O content was 8.9%. The kaolin is special for the catalytic cracking catalyst produced by Suzhou kaolin company, and the solid content of the kaolin is 78 weight percent. The rectorite is produced by Hubei's lucky famous rectorite development Co., ltd<3.5 wt%, al 2 O 3 The content of Na is 39.0 wt.% 2 The O content was 0.03 wt% and the solid content was 77 wt%. SB aluminium hydroxide powder, produced by Condex, germany, al 2 O 3 The content was 75% by weight. Gamma-alumina, manufactured by Condex, germany, al 2 O 3 The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, produced by Beijing chemical plant.
The phosphor-aluminum inorganic Binder1 used in the examples was prepared as follows: 1.91 kg of pseudo-boehmite (containing Al) 2 O 3 1.19 kg), 0.56 kg of kaolin (dry basis 0.5 kg) and 3.27 kg of decationized water are beaten for 30 minutes, 5.37 kg of concentrated phosphoric acid (mass concentration 85%) is added into the slurry under stirring, the phosphoric acid adding speed is 0.04 kg of phosphoric acid/min/kg of alumina source, the temperature is raised to 70 ℃, and then the reaction is carried out for 45 minutes at the temperature, so that the phosphorus-aluminum inorganic binder is prepared. The material ratios are shown in Table 1.
The inorganic binders Binder2, binder3 and Binder4 were also prepared as described above, except for the differences in the proportions of the materials, which are shown in Table 1.
TABLE 1
Examples 1-20 provide catalytic cracking assistants of the present invention, and comparative examples 1-16 illustrate catalytic cracking assistants as a comparison. Examples 1 to 10 are microporous ZSM-5 molecular sieves, and examples 11 to 20 are multistage-pore ZSM-5 molecular sieves. Comparative example 8 is a catalytic cracking comparison aid of the prior art for preparing a microporous ZSM-5 molecular sieve, and comparative example 16 illustrates the prior art for preparing a catalytic cracking comparison aid of a hierarchical ZSM-5 molecular sieve.
Example 1-1
16.2g of diammonium phosphate (analytical grade, hereinafter referred to as "Sedrin light complex technology development Co., ltd.) was dissolved in 60g of deionized water, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, and 113g of HZSM-5 molecular sieve (supplied by Qilu Co., ltd., relative crystallinity of 91.1%, silica/alumina molar ratio of 24.1, na) was added 2 O content 0.039 wt%, specific surface area 353m 2 Per gram, total pore volume of 0.177ml/g, the same applies below), adopts an impregnation method to modify, impregnates for 2 hours at 20 ℃, mixes with kaolin and pseudo-boehmite, adds deionized water and aluminum sol to pulp for 120 minutes to obtain slurry with 30 weight percent of solid content, adds hydrochloric acid to adjust the pH value of the slurry to 3.0, then continues to pulp for 45 minutes, then adds phosphorus-aluminum inorganic Binder1, stirs for 30 minutes, spray dries the obtained slurry to form microspheres, applies pressure to the outside and adds water, processes for 0.5 hours under the atmosphere of 500 ℃, 0.5Mpa and 50 percent water vapor to obtain a catalytic cracking auxiliary sample, the serial number CEZ1-1, the proportion of which is 50 percent of molecular sieve, 23 percent of kaolin, 18 percent of Binder1 and pseudo-boehmite (with Al 2 O 3 5% by weight of aluminum sol (in terms of Al) 2 O 3 Calculated) 4%.
And (3) carrying out reaction performance evaluation on 100% of the balancing agent and the catalytic cracking auxiliary CEZ1-1 prepared by doping the balancing agent by adopting a fixed bed micro-reaction device so as to illustrate the catalytic cracking reaction effect of the catalytic cracking auxiliary.
The auxiliary CEZ1-1 was subjected to an aging treatment at 800℃under a 100% water vapor atmosphere for 17 hours. The aged CEZ1-1 was mixed with an industrial FCC balance catalyst (FCC balance catalyst of industrial brand DVR-3, light oil micro-reaction activity of 63). And (3) loading the mixture of the balancing agent and the auxiliary agent into a fixed bed micro-reaction reactor, and carrying out catalytic pyrolysis on the raw oil shown in table 2 under the evaluation condition that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the agent-oil ratio is 3.2. The results of the reaction are given in Table 3, which includes blank test reagents.
TABLE 2
Project Raw oil
Density (20 ℃), g/cm 3 0.9334
Refraction (70 ℃ C.) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Colloid 14.4
Asphaltenes <0.1
Freezing point, DEG C 34
Metal content, ppm
Ca 3.9
Fe 1.1
Mg <0.1
Na 0.9
Ni 3.1
Pb <0.1
V 0.5
C m％ 86.88
H m％ 11.94
S m％ 0.7
Carbon residue m% 1.77
Examples 1 to 2
The procedure is as in example 1-1 except that the phosphorus-modified molecular sieve is prepared by mixing diammonium hydrogen phosphate, HZSM-5 molecular sieve and water and slurrying, and then heating to 100deg.C and maintaining for 2 hr. A catalytic cracking auxiliary sample, numbered CEZ1-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 3.
Comparative example 1
The same as in example 1-1 was distinguished in that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing was carried out in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 3.
TABLE 3 Table 3
Example 2-1
The same as in example 1-1 except that 16.2g of diammonium hydrogen phosphate was dissolved in 120g of deionized water at 50℃and stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated at 20℃for 2 hours; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 600 ℃ under 0.5Mpa and 30% steam atmosphere. A catalytic cracking auxiliary sample, numbered CEZ2-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
Example 2-2
The procedure is as in example 2-1 except that the diammonium phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 70℃and maintained for 2 hours. A catalytic cracking auxiliary sample, numbered CEZ2-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
Comparative example 2
The procedure is as in example 2-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 4.
TABLE 4 Table 4
Example 3-1
The same as in example 1-1 except that 10.4g phosphoric acid was dissolved in 60g deionized water at room temperature, stirred for 2 hours to obtain a phosphorus-containing aqueous solution, then 113g HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated at 20℃for 4 hours; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 400 ℃ under 0.3Mpa and 100% steam atmosphere. A catalytic cracking auxiliary sample, numbered CEZ3-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
Example 3-2
The procedure is as in example 3-1, except that an aqueous solution of the phosphorus-containing compound at 80℃is contacted with the HZSM-5 molecular sieve heated to 80℃for 4 hours. A catalytic cracking auxiliary sample, numbered CEZ3-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
Comparative example 3
The procedure is as in example 3-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ3, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 5.
TABLE 5
Example 4-1
The same as in example 1-1 except that 8.1g of diammonium hydrogen phosphate was dissolved in 120g of deionized water at room temperature, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, modified by an impregnation method, and impregnated for 2 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2 hours at 300 ℃ under 0.4Mpa and 100% steam atmosphere. A catalytic cracking auxiliary sample, numbered CEZ4-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
Example 4-2
The procedure is as in example 4-1 except that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 90℃and maintained for 2 hours. A catalytic cracking aid sample, numbered CEZ4-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
Comparative example 4
The procedure of example 4-1 was repeated except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ4, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 6.
TABLE 6
Example 5-1
The same as in example 1-1 except that 8.5g of trimethyl phosphate was dissolved in 80g of deionized water at 90℃and stirred for 1 hour to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated for 8 hours at 20 ℃; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 4 hours at 500 ℃ under 0.8Mpa and 80% steam atmosphere. A catalytic cracking auxiliary sample, numbered CEZ5-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
Example 5-2
The procedure is as in example 5-1 except that trimethyl phosphate, HZSM-5 molecular sieve and water are mixed and slurried, and then the mixture is heated to 120℃and maintained for 8 hours. A catalytic cracking auxiliary sample, numbered CEZ5-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
Comparative example 5
The procedure is as in example 5-1, except that the conditions for calcination are atmospheric (apparent pressure 0 MPa) and air calcination in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ5, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 7.
TABLE 7
Example 6-1
The same as in example 1-1 except that 11.6g of boron phosphate was dissolved in 100g of deionized water at 100℃and stirred for 3 hours to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, and the mixture was modified by an impregnation method and impregnated at 20℃for 2 hours; externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 4 hours at 400 ℃ under 0.3Mpa and 100% steam atmosphere. A catalytic cracking auxiliary sample, numbered CEZ6-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
Example 6-2
The procedure is as in example 6-1 except that the boron phosphate, HZSM-5 molecular sieve and water are mixed and slurried and then heated to 150℃for 2 hours. A catalytic cracking auxiliary sample, numbered CEZ6-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
Comparative example 6
The procedure was as in example 6-1 except that the conditions for calcination were atmospheric (apparent pressure 0 MPa) and air-calcination in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ6, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 8.
TABLE 8
Example 7-1
The same as in example 1-1 except that 14.2g of triphenylphosphine was dissolved in 80g of deionized water at 100deg.C, stirred for 2 hours to obtain a phosphorus-containing aqueous solution, and 113g of HZSM-5 molecular sieve was added to modify by impregnation, and impregnated for 4 hours at 20deg.C; externally applying pressure and adding water, and performing pressurized hydrothermal roasting at 600 ℃ under 1.0Mpa and 30% steam atmosphere for 2h. A catalytic cracking auxiliary sample, numbered CEZ7-1, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
Example 7-2
The procedure is as in example 7-1 except that the boron phosphate, HZSM-5 molecular sieve and water are mixed and slurried and then heated to 150℃for 2 hours. A catalytic cracking aid sample, numbered CEZ7-2, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
Comparative example 7
The procedure of example 7-1 was repeated except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. A catalytic cracking aid comparative sample, numbered DCEZ7, was prepared.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 9.
TABLE 9
Comparative example 8
Comparative example 8 illustrates the conventional process of the prior art and the resulting phosphorus-containing modified ZSM-5 comparative sample.
The same as in example 1-2, except that 16.2g of diammonium phosphate was dissolved in 60g of deionized water, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, 113g of HZSM-5 molecular sieve was added, modified by an impregnation method, immersed at 100 ℃ for 2 hours, dried in an oven at 110 ℃ and baked in a muffle furnace at 550 ℃ under normal pressure (apparent pressure 0 Mpa), the obtained phosphorus-modified ZSM-5 molecular sieve sample was then mixed with kaolin and pseudo-boehmite, deionized water and alumina sol were added to pulp for 120 minutes to obtain a slurry with a solid content of 30 wt%, hydrochloric acid was added to adjust the pH of the slurry to 3.0, and then pulping was continued for 45 minutes, then phosphorus-aluminum inorganic Binder1 was added, stirred for 30 minutes, the obtained slurry was spray-dried and molded to obtain microspheres, and the microspheres were baked at 500 ℃ for 1 hour to obtain a catalytic cracking aid comparative sample, no. DCEZ8. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 10.
Table 10
Example 8-1
The same as in example 1-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. A catalytic cracking auxiliary agent, numbered CEZ8-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 8-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. A catalytic cracking auxiliary agent, numbered CEZ8-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-1
The same as in example 1-1 except that the phosphorus aluminum inorganic Binder3 was replaced. A catalytic cracking auxiliary agent, numbered CEZ9-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 9-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. A catalytic cracking aid, numbered CEZ9-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
Example 10-1
The same as in example 1-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. A catalytic cracking auxiliary agent, numbered CEZ10-1, was prepared. The evaluation was conducted in the same manner as in example 5-1, and the results are shown in Table 11.
Example 10-2
The same as in examples 1-2 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. A catalytic cracking auxiliary agent, numbered CEZ10-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 11.
TABLE 11
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Examples 11-20 illustrate the use of phosphorus modified, multi-pore ZSM-5 molecular sieves in catalytic cracking adjuvants of the invention.
Examples 11-1 to 17-1
Examples 11-1 to 17-1 correspond to examples 1-1 to 7-1, respectively, except that the HZSM-5 molecular sieve was a multi-pore ZSM-5 molecular sieve (Qilu division, china petrochemical catalyst Co., ltd., relative crystallinity 88.6%, silica/alumina mole ratio 20.8, na 2 O content of 0.017 wt% and specific surface area of 373m 2 Per gram, a total pore volume of 0.256ml/g, a mesoporous volume of 0.119ml/g, an average pore diameter of 5.8nm, the same applies below). The catalytic cracking auxiliary agent samples are prepared, and the numbers CEZ11-1 to 17-1 are used. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Examples 11-2 to 17-2
Examples 11-2 to 17-2 correspond to examples 1-2 to 7-2, respectively, in sequence, except that the HZSM-5 molecular sieve is replaced with a multi-stage pore ZSM-5 molecular sieve. The catalytic cracking auxiliary agent samples are prepared, and the numbers CEZ11-2 to 17-2 are used. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Comparative example 9 to comparative example 15
Comparative examples 9 to 15 correspond to comparative examples 1 to 7, respectively, in sequence, except that the HZSM-5 molecular sieve was replaced with a multi-pore ZSM-5 molecular sieve. The catalytic cracking auxiliary samples are prepared, and the numbers DCEZ 9-15 are obtained.
The evaluation was conducted in the same manner as in example 1-1, and the results are shown in tables 12 to 18.
Table 12
TABLE 13
TABLE 14
TABLE 15
Table 16
TABLE 17
TABLE 18
Comparative example 16
Comparative example 16 illustrates a conventional process of the prior art and the resulting comparative aid sample of phosphorus-modified, multi-pore ZSM-5. The same as in comparative example 8, except that the HZSM-5 molecular sieve was replaced with a multi-stage pore ZSM-5 molecular sieve. A comparative sample of catalytic cracking aid, number DCEZ16, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 19.
TABLE 19
Example 18-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. A catalytic cracking auxiliary agent, numbered CEZ18-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 18-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 2. A catalytic cracking auxiliary agent, numbered CEZ18-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 19-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. A catalytic cracking aid, numbered CEZ19-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 19-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 3. A catalytic cracking aid, numbered CEZ19-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-1
The same as in example 11-1 except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. A catalytic cracking auxiliary agent, numbered CEZ20-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Example 20-2
The same as in example 11-2, except that the phosphorus aluminum inorganic Binder was replaced with Binder 4. A catalytic cracking auxiliary agent, numbered CEZ20-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 20.
Table 20
Example 21-1
The same as in example 1-1 was found to be different in that the addition of pseudo-boehmite and alumina sol was increased instead of the phosphor-alumina inorganic Binder1. A catalytic cracking auxiliary sample, numbered CEZ21-1, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 21.
Example 21-2
The same as in example 11-1 was found to be different in that the addition of pseudo-boehmite and alumina sol was increased instead of the phosphor-alumina inorganic Binder1. A catalytic cracking auxiliary sample, numbered CEZ21-2, was prepared. The evaluation was conducted in the same manner as in example 1-1, and the results are shown in Table 21.
Table 21
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Claims (32)

1. The preparation method of the catalytic cracking auxiliary agent is characterized by comprising the following steps: the MFI molecular sieve with the temperature of 50-150 ℃ and the aqueous solution of the phosphorus-containing compound with the temperature of 50-150 ℃ are immersed to obtain the phosphorus-modified MFI molecular sieve, the binder and the second clay which is optionally added are mixed, beaten and molded; carrying out hydrothermal roasting treatment on the molded product under external pressure and an atmosphere environment of externally added aqueous solution; the apparent pressure of the hydrothermal roasting treatment is 0.1-1.0 Mpa and the apparent pressure contains 1-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃.
2. The process according to claim 1, wherein the catalytic cracking aid comprises, on a dry basis, 5 to 75% by weight of the phosphorus-modified MFI molecular sieve, 1 to 40% by weight of the binder and 0 to 65% by weight of the second clay.
3. The process according to claim 1, wherein the phosphorus-containing compound is selected from the group consisting of organic phosphides and/or inorganic phosphides.
4. The process according to claim 3, wherein the organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphine bromide, triphenyl butyl phosphine bromide, triphenyl benzyl phosphine bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphoric, 1, 3-xylyl bistriethyl phosphorus; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
5. The process according to claim 1, wherein in the MFI molecular sieve, na 2 O<0.1 wt%。
6. The process according to claim 1, wherein the phosphorus-modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve.
7. The process according to claim 6, wherein the microporous ZSM-5 molecular sieve has a silica to alumina molar ratio of 15 to 1000; the ratio of mesoporous volume to total pore volume of the multistage hole ZSM-5 molecular sieve is more than 10%, the average pore diameter is 2-20 nm, and the mol ratio of silicon oxide to aluminum oxide is 15-1000.
8. The process according to claim 7, wherein the microporous ZSM-5 molecular sieve has a molar ratio of silica to alumina of 20 to 200; the mole ratio of the silicon oxide to the aluminum oxide of the multistage hole ZSM-5 molecular sieve is 20-200.
9. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to the aluminum is 0.01 to 2.
10. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to aluminum is 0.1 to 1.5.
11. The process according to claim 1, wherein the molar ratio of the phosphorus-containing compound to the MFI molecular sieve to aluminum is 0.2 to 1.5.
12. The preparation method according to claim 1, wherein the impregnation is carried out for 0.5 to 40 hours with a water sieve weight ratio of 0.5 to 1.
13. The process according to claim 12, wherein the impregnation treatment is carried out at 70 to 130 ℃.
14. The preparation method according to claim 1, wherein the binder is at least one selected from the group consisting of pseudo-boehmite, alumina sol, silica alumina sol, water glass and phosphorus-aluminum inorganic binder.
15. The method of claim 1 wherein said binder comprises a phosphorus aluminum inorganic binder.
16. The method of claim 1 wherein the binder is a phosphorus aluminum inorganic binder.
17. The method according to any one of claims 14 to 16, wherein the phosphorus-aluminum inorganic binder is a phosphorus-aluminum gel and/or a phosphorus-aluminum inorganic binder containing a first clay.
18. The process according to claim 17, wherein the first clay-containing phosphorus-aluminum inorganic binder comprises, on a dry basis, an aluminum-based binder comprising 2 O 3 15-40 wt% of aluminum component, calculated as P 2 O 5 45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay, wherein the phosphorus-aluminum inorganic binder P/Al weight ratio containing the first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.
19. The preparation method according to claim 1, wherein the second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomaceous earth.
20. The preparation method according to claim 14, wherein the binder comprises 3 to 39% by weight of the phosphorus-aluminum inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from the group consisting of pseudo-boehmite, alumina sol, silica-alumina sol and water glass on a dry basis, based on the total amount of the catalytic cracking auxiliary agent.
21. According to claimThe method of preparing of claim 17, further comprising: the phosphorus aluminum inorganic binder containing the first clay is prepared by the following steps: pulping and dispersing an alumina source, the first clay and water into slurry with a solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide is prepared by using 15-40 parts by weight of Al 2 O 3 An alumina source in an amount of greater than 0 parts by weight and no more than 40 parts by weight, based on dry weight of the first clay; adding concentrated phosphoric acid to the slurry with stirring according to the weight ratio of P/Al=1-6, and reacting the obtained mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus in phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.
22. The process according to claim 1, wherein the shaping is spray-drying shaping.
23. The process according to claim 1, wherein the apparent pressure of the atmosphere is 0.1 to 0.8Mpa.
24. The process according to claim 1, wherein the apparent pressure of the atmosphere is 0.3 to 0.6Mpa.
25. The process according to claim 1, wherein said atmosphere comprises 30% to 100% of water vapor.
26. The process according to claim 1, wherein said atmosphere comprises 60% to 100% water vapor.
27. The process according to claim 23, wherein the hydrothermal calcination treatment is performed at 300 to 500 ℃.
28. A catalytic cracking aid prepared by the method of any one of claims 1-27.
29. A method for catalytic cracking of hydrocarbon oils, the method comprising: contacting a hydrocarbon oil with the catalytic cracking aid of claim 28 under catalytic cracking conditions.
30. The method of claim 29, wherein the method comprises: contacting the hydrocarbon oil with a catalyst mixture comprising the catalytic cracking aid and a catalytic cracking catalyst under the catalytic cracking conditions; the content of the catalytic cracking auxiliary agent in the catalyst mixture is 0.1-30 wt%.
31. The method of claim 29 or 30, wherein the catalytic cracking conditions comprise: the reaction temperature is 500-800 ℃; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, straight-run wax oil, light/heavy propane deoiling, coker wax oil and coal liquefied products.
32. A preparation system for the preparation method of the catalytic cracking auxiliary agent in claim 1, which is characterized in that the system mainly comprises a phosphorus modification device, a raw material mixing device, a forming device and a pressurized hydrothermal roasting device of an MFI molecular sieve; wherein,
the phosphorus modification device of the MFI molecular sieve comprises phosphorus-containing compound solution introducing equipment;
the raw material mixing device receives raw materials of preparation auxiliary agents including the MFI molecular sieve subjected to impregnation treatment obtained from the phosphorus modification device of the MFI molecular sieve, the phosphorus-aluminum inorganic binder from the phosphorus-aluminum inorganic binder treatment device and optionally added clay;
the forming device is a spray drying forming device;
the pressurized hydrothermal roasting device is provided with an aqueous solution inlet and a gas pressurizing interface, and the apparent pressure of the hydrothermal roasting device is 0.1-1.0 Mpa and contains 1-100% of water vapor.
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